Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/69—Polymers of conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/71—Monoisocyanates or monoisothiocyanates
  • C08G18/715—Monoisocyanates or monoisothiocyanates containing sulfur in addition to isothiocyanate sulfur

Definitions

• ABSTRACT Ethylenically unsaturated polymers containing units wherein Y has the above meaning and X is SO C1 or H, or in the presence of a radical-forming initiator, so as to obtain modified polymers containing units with the formula wherein Y has the above meaning, the polymers thus obtained being elastomeric, resinous or fibrous and having improved physical and chemical properties.
• this invention relates to the fixing of reactive polar groups on a macromolecular chain through the addition of chlorosulfonyl isocyanate C l S-NCO upon the double bonds of ethylenically unsaturated polymers (ethylenically unsaturated polymers).
• Y stands for hydrogen, halogen alkyl (particularly methyl) or aryl, or any other organic group.
• Formula 1 corresponds to the reaction products of chlorosulfonyl isocyanate upon unsaturated polymers without a catalyst.
• X stands for the sulfochloride group or hydrogen.
• Formula 11 corresponds to the reaction products of chlorosulfonyl isocyanate upon unsaturated polymers in the presence of radical-forming initiators (radicalforming catalysts or ultraviolet rays).
• the unsaturated polymers which canundergo such chemical modification have a wide range of molecular weights and generally contain units with the formula wherein Y has the above-mentioned meaning. They belong to the diene homopolymer class (eg butadiene, isoprene, chloroprene, piperylene homopolymers) or to the diene-alkene co polymer class (with comonomers such as styrene, isobutylene, acrylonitrile). Natural products such as rubber, gutta-percha, terpenes, which contain units Ill and therefore answer the above gen eral definition, may be used within the scope of the invention. All such polymers may be used in the vulcanized state.
• diene homopolymer class eg butadiene, isoprene, chloroprene, piperylene homopolymers
• diene-alkene co polymer class with comonomers such as styrene, is
• the conditions of the reaction make it possible to avoid the degradation of the polymer thus treated.
• the method according to the invention is usually carried out at low or medium temperature (between 20C and +150C), more particularly between +10C and +C.
• the polymer to be modified is dissolved in a dry solvent or mixture of solvents; the concentration of the dissolved polymer varies between 1% and 15% by weight.
• the solvents used should be inert towards chlorosulfonyl isocyanate.
• the preferred solvents are chlorinated solvents, cyclohexane, aliphatic hydrocarbons, ethers, etc. Dispersions of rubber in the said solvents may be used, for instance when starting from regenerated or unregenerated vulcanized rubbers.
• solvent and polymer are dried by conventional physical or chemical means before they are brought together. Atmospheric oxygen is eliminated from the reaction space through displacement by an inert gas such as deoxygenized nitrogen or argon.
• radical-forming compounds such as azoic compounds, notably azo-diisobutyronitrile, are used.
• concentration of such initiators varies between 0.1% and 5% on the weight of the dissolved polymer.
• the polymer (and the catalyst, if any) are dissolved in the solvent, and a solution of chlorosulfonyl isocyanate in the same solvent is added, e.g. a 10% by weight solution of chlorosulfonyl isocyanate in cyclohexane. This is done slowly, with stirring. The mixture is then allowed to stand for a period of 30 minutes to 24 hours. However, the reaction is usually ended when the reagents have been in contact for 5 to 6 hours. The mixture usually solidifies more or less quickly and completely, according to the extent of the modification. The modified polymer is separated by filtration or by precipitation with a non-solvent. The excess reagent (chlorosulfonyl isocyanate) is thereafter eliminated through extraction of the raw product with cyclohexane. The purified product is then dried under vacuum at room temperature.
• a solution of chlorosulfonyl isocyanate in the same solvent is added, e.g. a 10% by weight solution of
• the residual cyclohexane and the ketone are eliminated by distillation, and may be condensed, purified and recycled.
• the modified polymer gradually precipitates It is separated by filtration, thoroughly washed with water and dried under vacuum.
• reaction products containing units 1 or 11 Numerous chemical reactions may be applied to the reaction products containing units 1 or 11, so that the method according to the invention makes it possible to prepare a wide range of novel materials, having a wide range of practical uses.
• the level of modification and the nature of the chemical functions introduced, elastomeric, resinous or fibrous products may be obtained.
• Macromolecular structures are thus formed in which a number of isoprene units bear lactam groups (structure I) regularly arranged. This result in high strength properties, notably in a high modulus of elasticity.
• the polymers thus obtained contain both the hydrocarbon skeleton of conventional elastomers and polyamide groups which ensure the cohesion of the whole, as in the case of textile fibres. It will readily be understood that with higher levels of modification, the product changes from a flexible elastomer to a more rigid, high-strength polymer.
• the different chemical structures obtained allow functional reticulation through covalent or ionic bonds.
• the vulcanisates thus obtained have good heat strength, good ageing strength, and stand up well to degradation by chemicals or solvents.
• the modified products Due to their high polarity, the modified products are compatible with a large number of materials and of inorganic or organic fillers. Consequently, the products modified with chlorosulfonyl isocyanate are highly adhesivating towards the main substrates: wood, glass, metals, textiles, etc..
• the treatment described herein makes it possible to modify the surface properties of vulcanized rubber mouldings, for instance greatly to lower the coefficient of friction, which is desirable for many uses.
• the amount of reagent used in this example corresponds to a molecular ratio r 0.1 (r p.M/m.P, with m 141.5 molecular weight of the isocyanate, p weight of isocyanate used, M molecular weight of polymer chain unit 68 for polyisoprenes, P weight of polymer used).
• the reaction was continued for 5 hours with stirring at 25C.
• the reaction mixture gelled gradually.
• the reaction product was then separated by filtration, then extracted in a Soxhlet with cyclohexane to eliminate traces of uncombined reagent.
• the polymer was then dried under vacuum at room temperature, and its elementary composition was determined.
• chlorosulfonyl isocyanate was reacted upon butyl rubber (random copolymer of 96.5% isobutylene and 3.5% isoprene).
• the reagent settled exclusively on the isoprene groups in the chain, giving structures of type I (n 1, X SO Cl).
• the amount of reagent added was therefore approximately 10%.
• Infrared stectrography showed structures which were different from those obtained without a radical-forming initiator.
• the structure of the product was the same as for the polymers prepared with ultraviolet illumination (Example 8).
• Example 8 The procedure was the same as in Example 8, but with a random copolymer of 65% butadiene and 35% acrylonitrile instead of polybutadiene. To a solution of 45 g copolymer in 2,250 ml anhydrous chloroform were added 77 g chlorosulfonyl isocyanate dissolved in 150 ml chloroform. The mixture was illuminated with ultraviolet light at room temperature for 16 hours.
• Example 8 The procedure was the same as in Example 8, but with a trisequential styrenebutadiene-styrene block copolymer instead of polybutadiene. An unpurified commercial product was used.
• the fibrous polymer obtained had the following composition:
• This example relates to a special type of hydrolysis of the products obtained in examples l-2-3.
• Example 6 The procedure was similar to Example 6, but with caustic soda instead of sodium bicarbonate. g natural polyisoprene modified with isocyanate (r 0.5, t 41.7) were dissolved in 700 ml acetone. The solution was slowly stirred into a solution of 100 g caustic at C. The product swelled greatly in water and adhered strongly notably to glass and wood. It was washed with methanol and dried under vacuum.
• Example 12 10 g of the polymer obtained in Example 12 were dispersed in a 36.5 g/l solution of hydrochloric acid. The mixture was heated at 70C for 2 hours. Under such At 410C, the control polyisoprene is almost entirely destroyed, while the modified polyisoprene retains 40% of its initial weight.
• EXAMPLE 14 This example relates to the preparation of a novel product through substitution of the chlorine atoms in the structures described in Examples 1 to 3.
• a 100 Example 2 were d1ssolved 1n 600 ml acetone.
• the solu- 20 Polyisoprene B 100 100 tion was introduced into a vessel fitted with a reflux Magnesium wide l0 condenser protected against moisture and a dropping g i g L5 funnel. 160 ml aniline were added through the latter.
• EXAMPLE 15 With unfilled formulations, the vulcanisates then Temperature (C) Loss of weight modified control polyisopre ne polyisoprene have high modulus, low elongation and good solvent swelling strength.
• Polyisoprene B (vulcanized 30 mins at 150C):
• chlorosulfonyl isocyanate is reacted with any one of the abovementioned polymers, but after they have been vulcawherein Y is a hydrogen atom, a halogen atom, an alkyl group or an aryl group, and X is sulfochloride group 50 C], as produced by the method comprising reacting an ethylenically unsaturated polymer containing Cl-lnized.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Cited By (2)

• 1971
  • 1971-04-08 FR FR7112504A patent/FR2133119A5/fr not_active Expired
• 1972
  • 1972-04-05 US US00241438A patent/US3855348A/en not_active Expired - Lifetime
  • 1972-04-06 GB GB1592772A patent/GB1357843A/en not_active Expired
  • 1972-04-07 DE DE19722216893 patent/DE2216893A1/de active Pending

Non-Patent Citations (1)

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